LAUSR

In the present work, we investigate at the density functional theory (DFT) level, two-dimensional (2D) conjugated polymers based on C3-symmetric truxene-based cores. In total, 27 different 2D polymers have been exhaustively studied with the aim to explore the impact that the following effects exert on the electronic and charge-transport properties: (i) the nature of the conjugated platform, going from electron-rich truxene (Tx) and triindole (Tr) units to electron-deficient truxenone (To) cores, (ii) the spacing of the cores with different π-bridges, i.e., phenylene (Ph) or ethynylene (A) units, (iii) the effect of the linker position (2,7,12-susbtitution in T2 polymers and 3,8-13-substitutionin T3 polymers), and (iv) the increased number of π-bridges conecting the cores from three in T2 and T3 to six linkers in T2,3. To this end, we have carried out a large battery of DFT calculations on fragments extracted from the 2D polymers (dimers and trimers), as well as on the corresponding periodic 2D structures (infinite monolayer and self-assembled monolayers) by using periodic boundary conditions. Our results show that a simultaneous manipulation of pore surface and band gap enginering together with charge-transport parameters can be achieved in these truxene-based 2D polymers by fine-tuning their structural features. Thus, this study provides interesting guidelines for the design of new promising 2D conjugated polymers with exceptional electronic properties, which can be adjusted according to the targeted funcionality.